Process for permanently pressing textile articles made of keratinic fibers

ABSTRACT

THE METHOD OF PERMANENTLY PRESSING TEXTILE ARTICLES CONTAINING KERATINIC FIBER, WHICH COMPRISES THE STEPS OF IMPREGANTING THE TEXTILE ARTICLE WITH A SOLUTION CONTAINING EFFECTIVE AMOUNTS OF A WATER SOLUBLE POLYMER HAVING BRANCHED CHAINS HAVING TERMINAL-SH FUNCTIONAL GROUPS, PLACING THE IMPREGNATED TEXTILE ARTICLE IN THE CONFIGURATION CORRESPONDING TO THE SHAPE DESIRED, AND THEN PRESSING THE AREA IN WHICH A CREASE IS DESIRED AT AN ELEVATED TEMPERATURE.

United States Patent 3,576,592 PROCESS FOR PERMANENTLY PRESSING TEXTILE ARTICLES MADE OF KERATINIC FIBERS Charles Zviak, Franconville, and Andre Viout, Paris, France, assignors to Societe Anonyme dite: LOreal No Drawing. Filed Feb. 21, 1966, Ser. No. 528,762 Claims priority, application France, Feb. 23, 1965,

90; Aug. 5, 1965, 27,374 Int. Cl. C09k 3/30; D06m /12 US. Cl. 8-1276 2 Claims ABSTRACT OF THE DISCLOSURE The method of permanently pressing textile articles containing keratinic fibers, which comprises the steps of impregnating the textile article with a solution containing effective amounts of a water soluble polymer having branched chains having terminal SH functional groups, placing the impregnated textile article in the configuration corresponding to the shape desired, and then pressing the area in which a crease is desired at an elevated temperature.

It is known that it is desirable to impress creases in the most durable manner possible on textile articles, for example, creases in pants or in pleated skirts.

The present invention relates to a new process for permanently pressing cloth or knitted materials made of wool, so that it will be resistant to wrinkles and permanently retain creases made therein at the time of treatment.

These creases may be obtained according to the invention in a simple and durable manner without causing damage to or weakening of the physical properties of the textile articles.

One object of the present invention is to present a new process for making creases in textile articles made of keratinic fibers, this new process being characterized by the fact that the above-mentioned textile articles are impregnated with a basic solution of polysulfhydrylated polymers, then heated and pressed in the area in which a crease is desired, for example, by using an iron.

According to the invention, the solution to be applied to the textile article contains about 1 to and preferably from 2 to 6% by weight of polysulfhydrylated polymers.

The pH of this solution is between about 3.5 and 10 and is preferably between 9 and 9.5.

Among the polysulfhydrylated polymers which can be used to carry out the process according to the invention, are the polysulfhydrylated polymers corresponding to the following formula:

R!!! CH-(J CH-CH- 611 int in which:

Patented Apr. 27, 1971 ice or a --OCOCH radical, or a COOCH radical, or a CN radical, n is a whole number.

The polysulfhydrylated polymers are of the formula:

in which:

R is a hydrogen atom or a lower alkyl such as CH or C H or a lower hydroxy alkyl such as R is a hydrogen atom or a -CH radical,

q is a whole number between 2 and 6, inclusive,

p is a whole number equal to 0 or 1,

R and R" are hydrogen atoms or lower alkyl radicals, or phenyl radicals, or lower alkyloxy radicals, R and R being the same or different,

R" is a hydrogen atom, or the -OCOCH radical, or the CEN radical, or the COOCH radical,

n is a whole number.

The polysulfhydrylated polymers are of the formula:

IIZII RI! CH-(IJ(IZH---CH-CH(IJCH-CH R R COOH o0 R R COOH ([30 Q. Q, n

in which:

R and R" which may be the same or different are hydrogen atoms, or lower alkyl radicals, or phenyl radicals, or lower alkyloxy radicals,

R" is a hydrogen atom, or the OCOCH radical, or

the COOCH radical, or the --CEN radical,

n is a whole number,

Q is a radical represented by the following formula:

in which:

R1 is H or CH3,

R is H or COOH,

q is a whole number from 1 to 5, inclusive,

q is equal to 0 or 1,

p is equal to 0 or 1,

Q is a radical represented by the following formula:

in which:

R is a hydrogen atom or a lower alkyl,

R, is a lower alkyl, or a radical or formula r and r being the same or different lower alkyls, or being part of a heterocyclic ring such as that of morpholine or piperidine, m is a whole number equal to 2, 3 or 4.

The polysulfhydrylated polymers are constituted by an anhydride homopolymer on which at least one mercapto-amine is condensed.

The homopolymer may be a maleic polyanhydride polymer, an itaconic polyanhydride polymer, an acrylic polyanhydride polymer, a mixed acrylic-methacrylic polyanhydride polymer, or a methacrylic polymer, although this list is not exhaustive.

Aminothiols having the following formula may be used to sulfhydrylate these homopolymers:

R is an alkylene radical comprising preferably from 2 to 4 carbon atoms, which may be substituted by lower alkyls which may have up to 4 carbon atoms, or a carboxyl radical, or a carbalkyloxy group, and

R is a hydrogen atom or a lower alkyl such as CH Among the aminothiols corresponding to the above formula, these may be cited as examples:

fi-mercaptoethylamine, cysteine, and ethyl cysteinate.

Mercapto-amide amines of the following formula may also be used to sulfhydrylate the homopolymers:

in which:

R is H, --CH C H or CH CH OH, R is H or -COOH, q is a whole number between 1 and 5, inclusive, q is equal to 0 or 1, p is equal to O or 1.

Among the mercapto-amide amines corresponding to this last formula may be cited those which are obtained from esters of thioglycolic acid, thiolactic acid or ,B-mercaptopropionic acid and from diamines such as ethylene diamine, hexamethylene diamine, N-hydroxyethyl ethylene diamine.

It is equally possible to condense amines not made up of SH groups on the anhydride homopolymers, with simultaneous condensation of the mercapto-amines.

Another object of the present invention is to provide a new article of manufacture which consists of a composition for permanently creasing textile articles made from keratinic fibers. This composition is essentially characterized by the fact that it contains at least one polysulfhydrylated polymer and a base, the pH of this composition being between about 3.5 and and being preferably between 9 and 9.5.

In a preferred method of treating with aforementioned composition this last is placed in an aerosol bomb with a liquified gas propellant under pressure, from which it is permitted to escape as a lather or a jet of liquid which may be atomized.

In order that the invention may be better understood, several embodiments thereof will now be described, purely by way of example, without limiting the scope of the invention to the specific details thereof.

mercaptoethylamine with the styrene/maleic anhydride copolymer sold by the Texas Butadiene Chemical Corp.

under the trademark Res l SMA 1000A having the formula:

CHCHzCH-CH- OOOH I00 1'; (1H,

CH2 SIH n De-ionized water--959 g.

Monethanol to bring the pH of the solution to 9.5 about 11 g.

The woolen cloth in which a permanent crease is desired is dampened with this solution; then the cloth is ironed to impress the crease using a hot iron and a damp cloth. 7

When the cloth has dried and cooled off, it has a permanent crease which remains even after several washings.

EXAMPLE 2 A composition to obtain permanent creases in textile articles of keratinic fibers is prepared as follows:

First solution A having the following composition is prepared:

A polysulfhydrylated polymer as in Example 1 above 40 Ammonia at 20 B. to bring the pH of the solution to 9.5, about cc 60 De-ionized water g 900 The following mixture is then placed in an aerosol container:

Solution A 70 Dichlorodifluoromethane 15 Trichloromonofluoromethane 15 To use the composition, which is in the form of an aerosol, the solution contained in the bomb is sprayed onto the textile article to be creased, then a crease is formed using a hot iron and a damp cloth.

EXAMPLE 3 To prepare a composition according to the invention in the form of a transient lather spread by an aerosol bomb, the following process is used:

First solution B having the following composition is prepared:

A polysulfhydrylated polymer as in Example 1 above g 30 De-ionized Water g 920 Ammonia at 20 B. to bring the pH to 9.5,

about cc 45 Silicone anti-foaming agent g 4 Polyethoxyether of a fatty alcohol g 1 After this a mixture consisting of the following is placed in a special container:

G. Solution B Dichlorodifluoromethane 15 EXAMPLE 4 A composition according to the invention is obtained by mixing:

A polysulfhydrylated polymer obtained by condensation of a mol of fi-mercaptoethylamine on a mol of maleic anhydride/ ethylene copolymer sold by the Monsanto Corp. under the trademark Resin DX 840.11 having the formula:

Ammonia at 20 B. q.s.p. pH=9.3. Distilled water q.s.p. 100 cc.

20 A crease 1s made 1n a woolen cloth as in the preceding examples, using a hot iron and a damp cloth.

The permanent press thus obtained holds up well even when the cloth is placed in boiling water for an hour.

6 A polysulfhydrylated polymer as in Example 5 g 1.5 Ammonia at 20 B. q.s.p. pH 9.3. Silicone anti-foaming agent g 0.4 Water, q.s.p cc 100 The following mixture is then put in an aerosol container:

G. Solution C 85 Butane The contents of the areosol bomb are sprayed onto the cloth to be treated in the area where pressing is desired. A crease is formed using a hot iron and a damp cloth.

Good quality pressing is obtained.

EXAMPLE 7 A composition according to the invention which is in the form of a transient aerosol lather is made by first preparing a solution D having the following composition:

A polysulfhydrylated polymer obtained by condensing fi-mercaptoethylamine and N,N-diethyl-propylene diamine on an ethylene/maleic anhydride copolymer having the formula:

EXAMPLE 5 A solution having the following composition is placed in a roll-on-applicator:

A polysulfhydrylated polymer obtained by condensing a N-(fi-aminoethyl) thioglycolamide on a ethylene/maleic anhydride copolymer sold under the trademark Resin DX.840.11 by the Monsanto Chemical Co., this polymer having the formula:

Ammonia at B. q.s.p. pH=9.3. Distilled water q.s.p. 100 cc.

The cloth to be treated is dampened by rolling the ball of the applicator over the area where pressing is desired, then ironing it with a hot iron.

Thus a crease with excellent holding power is obtained.

EXAMPLE 6 A composition according to the invention is made in the form of an aerosol by first preparing a solution C having the following composition:

Ammonia at 20 B. q.s.p. pH 9.3.

Silicone anti-foaming agent g 0.4 Polyethoxyether of alkylphenol g 0.2. Water, q.s.p cc 100 A mixture of the following is then placed in an aerosol bomb:

G. Solution D Dichlorodifluoromethane 15 The aerosol bomb has an atomizing valve which permits a ribbon of lather to be placed on the textile article to be treated, in the area of pressing. The lather disappears rapidly, impregnating the cloth below it with liquid.

Pressing is then done as in the preceding example, using a hot iron and a damp cloth and equally good results are obtained.

EXAMPLE 8 A composition is prepared by mixing:

A polysulfliydrylated polymer obtained by condensing B-mercaptoethylamine and n-butylamine on a vinyl acetate/maleic anhydride copolymer having the formula:

COOH CO OCOCHa 1|IH OCOCHs NH 3g.

CH2 0 H; 2 (EH: SH :1

Ammonia at 20 B. q.s.p. pH=9.3

75 Distilled water, q.s.p. cc.

Woolen cloth is pressed as in the preceding examples, using a hot iron and a damp cloth. The permanent press thus obtained holds up well, even when the cloth is immersed in hot water for an hour.

EXAMPLE 9 Ammonia at 20 B. q.s.p. pH=9.3 Distilled water, q.s.p. 100 cc.

A crease is made in a woolen cloth as in the preceding examples using a hot iron and a damp cloth; the crease thus obtained holds up well even when immersed in hot 'water for an hour, and remains after several washings.

EXAMPLE 10 A composition according to the invention is prepared by mixing:

A polysulfhydrylated polymer obtained by condensing fi-mercaptoethylamine on a maleic anhydride/vinyl acetate copolymer having the formula:

Ammonia at 20 B q.s.p. pH=9.3 Distilled water, q.s.p. 100 cc.

Using the same method as in the preceding examples, a permanent crease is obtained which holds up very well during several washings with very hot water.

EXAMPLE 11 I S H n De-ionized water 959 g. Monoethanolamine to bring the pH of the solution to 9.5 about 11 g.

The woolen cloth in which a permanent crease is desired is dampened with this solution. The cloth is ironed with a hot iron and a damp cloth to impress the crease nd a permanent crease is obtained which remains even ter several washings.

8 EXAMPLE 12 A composition to make permanent creases in textile articles made of keratinic' fibers is prepared as follows:

First a solution E having the following composition is prepared:

The polysulfhydrylated homopolymer mentioned in Example 11 g 40 Ammonia at 22 B. to bring the pH to 9.5,

about cc 65 De-ionized water, q.s.p g 1000 The following mixture is then placed in an aerosol bomb:

G. The aforementioned solution E 70 Dichlorodifiuoromethane 15 Trichloromonofluorornethane 15 To use the composition which is in the form of an aerosol, the solution contained in the bomb is sprayed onto the textile article at the place at which a crease is desired; then the crease is formed using a hot iron and a damp cloth.

EXAMPLE 13 To make a permanent crease in a textile article made of keratinic fibers, a solution having the following composition is placed in a roll-on applicator:

A polysulfhydrylated homopolymer having the formula:

CH CH CH--CH 30 OH 70 00 OH O O I IH NH 12 C|4HP 2 CH2 S H n Ammonia at 20 B. q.s.p. pH:9.3. Distilled water, q.s.p. cc.

The cloth to be treated is dampened by rolling the ball of the applicator over the area in which a crease is desired, then ironing with a hot iron.

A crease with excellent holding power is thus obtained. v t

It is clear that the process according to the invention permits the easy and efficient formation of creases in textile articles made of keratinic fibers such as wool.

It should be understood that the above-described embodiments of the invention may be modified as to detail without thereby going outside the scope of the invention.

In particular, it goes without saying that the crease may be formed in the textile article without using a hand iron by using another method such as a pressing machine which permits the simultaneous application of heat and pressure.

It goes equally without saying that the process according to the invention permits the formation of all sorts of creases in textile articles other than woven cloths. In particular, the process according to the invention permits the formation of creases in knitted materials, laces, felts and generally in keratinic textile fibers assembled in any manner whatever.

Finally, it is obvious that the process according to the invention is not limited to textile processes carried out using exclusively keratinic fibers such as wool, alpaca, camels hair or mohair, for treatment according to the invention may be possible even if these keratinic fibers are mixed with other natural, artificial or synthetic textile fibers.

What is claimed is:

1. A process for permanently pressing textile articles containing wool fibers which comprises impregnating the textile with an aqueous solution containing 1-20 weight of I-S, q is equal to or 1 and p is equal to O or I, O is a radical of the formula percent of a polysulfhydrylated polymer selected from the group consisting of:

(a) water-soluble polysulfhydrylated polymer having recurring units of the formula (0) a water-soluble polysulfhydrylated polymer having recurring units of the formula RI! RI! CH( J-CHCH-CH( J-CHOH f wherein R is selected from the group consisting of --CH-C OHCH hydrogen and lower alkyl, R is selected from the 0:9 group consisting of lower alkyl and 611 its I!L N I s11 wherein R is selected from the group consisting of Wherem alkylene having 2 to 4 carbon atoms, lower alkyl 15 T substituted lower alkylene, carboxy substituted lower alkylene and carbalkoxy substituted lower alkylene, I R is selected from the group consisting of hydrogen 7 and lower alkyl, R is selected from the group conis selected from the group consisting of lower alkyl i ti f hydrogen, lower lk l, h l d lower amines and a heterocyclic ring selected from the alkoxy, R" is selected from the group consisting of group Consisting of morpholino and Pipefidino rings hydrogen lower alkyl, phenyl and lower alkoxy and and m is anintegef of and R'" is selected from the group Consisting of (d) a water-soluble polysulfhydrylated polymer con- MOCOCHS, .COOCH3 and densed from (1) an anhydride polymer selected from (b) a water-soluble polysulfhydrylated polymer havthe group Consisting of P l/( y anhydride), P y ing r rrin it f th for l (itaconic anhydride) poly(mixed acrylic-methacrylic anhydride), poly(methacrylic anhydride) and poly (maleic anhydride), and (2) a member selected from the group consisting of Z (i) an aminothiol of the formula f= HS-RNRR' 0H N-R1 wherein R is selected from the group consisting of QQ lower alkylene having 2-4 carbon atoms, lower alkyl substituted lower alkylene, carboxy substituted lower 13:0 alkylene and carbalkoxy substituted lower alkylene and R is lower alkyl and E 2 (ii) a mercapto-amide amine of the formula R1 R2 sH 40 HN-oH- oHz)q[NH-oo-on(o1r2)p1q's1r wherein R is selected from the group consisting of wherein R is selected from the group consisting of hydrogen, CH -C H and --CH CH OH, R hydrogen, lower alkyl and hydroxy low r alkyl, R2 is selected from the group consisting of hydrogen and 1s selected from the group consisting of hydrogen -COOH, q is an integer of 1-5, q is equal to 0 or and s q is an integer of P is equal to 0 0r 1 and p is equal to 0 or 1, said solution having a 1, R and R" are selected from the group consisting H ranging from 35-10, placing the impregnated of hydrogen, lower alkyl, P y and lower Ys textile article in the configuration corresponding to and R i Selected from the g p consisting of ythe shape desired and pressing said textile article at a, and a an elevated temperature.

2. The process of claim 1 wherein the water-soluble polysulfhydrylated polymer defined in (d) is additionally condensed from (3) a lower alkyl amine.

References Cited 1 I l R 000E UNITED STATES PATENTS Q 2,238,672 4/1941 Arthur et al. s-12s wherein R and R" are selected from the group con- 2,933,409 4/ 1960 Binkley 6t 8 sisting of hydrogen, lower alkyl, phenyl and lower 3,148,127 9/1964 Marsh 252--305X alkoxy, R' is selected from the group consisting of 7 9 M s e et a1 167-87.1 hydrogen, OCOCH -COOCH and -CEN, Q is a radical of the formula O E N PATENTS R1 1,349,140 12/1963 France 26079 N Z)QIN O 0c 0H2 .,1q- RICHARD D. LOVERING, Primary Examiner wherein R is selected from the group consisting of US. Cl. X.R.

hydrogen and -CH R is selected from the group consisting of hydrogen and -COOH, q is an integer 

